Ruthenium-Alloy Electrocatalysts with Tunable Hydrogen Oxidation Kinetics in Alkaline Electrolyte
Abstract
High-surface-area ruthenium-based RuxMy (M = Pt or Pd) alloy catalysts supported on carbon black were synthesized to investigate the hydrogen oxidation reaction (HOR) in alkaline electrolytes. The exchange current density for hydrogen oxidation on a Pt-rich Ru0.20Pt0.80 catalyst is 1.42 mA/cm2, nearly 3 times that of Pt (0.490 mA/cm2). Furthermore, RuxPty alloy surfaces in 0.1 M KOH yield a Tafel slope of ~30 mV/dec, in contrast with the ~125 mV/dec Tafel slope observed for supported Pt, signifying that hydrogen dissociative adsorption is rate-limiting rather than charge-transfer processes. Ru alloying with Pd does not result in modified kinetics. We attribute these disparate results to the interplay of bifunctional and ligand effects. Here, the dependence of the rate-determining step on the choice of alloy element allows for tuning catalyst activity and suggests not only that a low-cost, alkaline anode catalyst is possible but also that it is tantalizingly close to reality.
- Authors:
-
- Univ. of Tennessee, Knoxville, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1186926
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 24; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; palladium; platinum; metal nanoparticles; alloys; catalysts
Citation Formats
St. John, Samuel, Atkinson, III, Robert W., Unocic, Raymond R., Zawodzinski, Jr., Thomas A., and Papandrew, Alexander B. Ruthenium-Alloy Electrocatalysts with Tunable Hydrogen Oxidation Kinetics in Alkaline Electrolyte. United States: N. p., 2015.
Web. doi:10.1021/acs.jpcc.5b03284.
St. John, Samuel, Atkinson, III, Robert W., Unocic, Raymond R., Zawodzinski, Jr., Thomas A., & Papandrew, Alexander B. Ruthenium-Alloy Electrocatalysts with Tunable Hydrogen Oxidation Kinetics in Alkaline Electrolyte. United States. https://doi.org/10.1021/acs.jpcc.5b03284
St. John, Samuel, Atkinson, III, Robert W., Unocic, Raymond R., Zawodzinski, Jr., Thomas A., and Papandrew, Alexander B. Thu .
"Ruthenium-Alloy Electrocatalysts with Tunable Hydrogen Oxidation Kinetics in Alkaline Electrolyte". United States. https://doi.org/10.1021/acs.jpcc.5b03284. https://www.osti.gov/servlets/purl/1186926.
@article{osti_1186926,
title = {Ruthenium-Alloy Electrocatalysts with Tunable Hydrogen Oxidation Kinetics in Alkaline Electrolyte},
author = {St. John, Samuel and Atkinson, III, Robert W. and Unocic, Raymond R. and Zawodzinski, Jr., Thomas A. and Papandrew, Alexander B.},
abstractNote = {High-surface-area ruthenium-based RuxMy (M = Pt or Pd) alloy catalysts supported on carbon black were synthesized to investigate the hydrogen oxidation reaction (HOR) in alkaline electrolytes. The exchange current density for hydrogen oxidation on a Pt-rich Ru0.20Pt0.80 catalyst is 1.42 mA/cm2, nearly 3 times that of Pt (0.490 mA/cm2). Furthermore, RuxPty alloy surfaces in 0.1 M KOH yield a Tafel slope of ~30 mV/dec, in contrast with the ~125 mV/dec Tafel slope observed for supported Pt, signifying that hydrogen dissociative adsorption is rate-limiting rather than charge-transfer processes. Ru alloying with Pd does not result in modified kinetics. We attribute these disparate results to the interplay of bifunctional and ligand effects. Here, the dependence of the rate-determining step on the choice of alloy element allows for tuning catalyst activity and suggests not only that a low-cost, alkaline anode catalyst is possible but also that it is tantalizingly close to reality.},
doi = {10.1021/acs.jpcc.5b03284},
journal = {Journal of Physical Chemistry. C},
number = 24,
volume = 119,
place = {United States},
year = {Thu May 21 00:00:00 EDT 2015},
month = {Thu May 21 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 72 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism
journal, January 2014
- Durst, J.; Siebel, A.; Simon, C.
- Energy Environ. Sci., Vol. 7, Issue 7
Study of the Exchange Current Density for the Hydrogen Oxidation and Evolution Reactions
journal, January 2007
- Neyerlin, K. C.; Gu, Wenbin; Jorne, Jacob
- Journal of The Electrochemical Society, Vol. 154, Issue 7
Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs
journal, March 2005
- Gasteiger, Hubert A.; Kocha, Shyam S.; Sompalli, Bhaskar
- Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 9-35
Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis
journal, June 2013
- Cui, Chunhua; Gan, Lin; Heggen, Marc
- Nature Materials, Vol. 12, Issue 8
Octahedral PtNi Nanoparticle Catalysts Exceptional Oxygen Reduction Activity by Tuning the Alloy Particle Surface Composition
journal, October 2012
- Cui, Chunhua; Gan, Lin; Li, Hui-Hui
- Nano Letters, Vol. 12, Issue 11, p. 5885-5889
Anion-exchange membranes in electrochemical energy systems
journal, January 2014
- Varcoe, John R.; Atanassov, Plamen; Dekel, Dario R.
- Energy & Environmental Science, Vol. 7, Issue 10, p. 3135-3191
Oxygen Reduction on Silver Low-Index Single-Crystal Surfaces in Alkaline Solution: Rotating Ring DiskAg(hkl) Studies
journal, March 2006
- Blizanac, B. B.; Ross, P. N.; Marković, N. M.
- The Journal of Physical Chemistry B, Vol. 110, Issue 10, p. 4735-4741
Kinetics of the Hydrogen Oxidation/Evolution Reaction on Polycrystalline Platinum in Alkaline Electrolyte Reaction Order with Respect to Hydrogen Pressure
journal, January 2014
- Rheinländer, Philipp J.; Herranz, Juan; Durst, Julien
- Journal of The Electrochemical Society, Vol. 161, Issue 14
Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption
journal, February 2013
- Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao
- Nature Chemistry, Vol. 5, Issue 4
LEIS and AES on sputtered and annealed polycrystalline Pt-Ru bulk alloys
journal, August 1993
- Gasteiger, H. A.; Ross, P. N.; Cairns, E. J.
- Surface Science, Vol. 293, Issue 1-2
Water dissociation on well-defined platinum surfaces: The electrochemical perspective
journal, March 2013
- van der Niet, Maria J. T. C.; Garcia-Araez, Nuria; Hernández, Javier
- Catalysis Today, Vol. 202
Adsorption of phosphate species on poly-oriented Pt and Pt(111) electrodes over a wide range of pH
journal, November 2010
- Gisbert, Rubén; García, Gonzalo; Koper, Marc T. M.
- Electrochimica Acta, Vol. 55, Issue 27
Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy
journal, January 2015
- Sheng, Wenchao; Zhuang, Zhongbin; Gao, Minrui
- Nature Communications, Vol. 6, Issue 1
Pt–Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or electronic effect?
journal, January 2015
- Wang, Ying; Wang, Gongwei; Li, Guangwei
- Energy & Environmental Science, Vol. 8, Issue 1
Electrooxidation of adsorbed CO on Pt(111) and Pt(111)/Ru in alkaline media and comparison with results from acidic media
journal, July 2004
- Spendelow, J. S.; Lu, G. Q.; Kenis, P. J. A.
- Journal of Electroanalytical Chemistry, Vol. 568
High performance of Ru nanoparticles supported on carbon for anode electrocatalyst of alkaline anion exchange membrane fuel cell
journal, March 2013
- Ohyama, Junya; Sato, Takuma; Satsuma, Atsushi
- Journal of Power Sources, Vol. 225
H2 and CO Electrooxidation on Well-Characterized Pt, Ru, and Pt-Ru. 2. Rotating Disk Electrode Studies of CO/H2 Mixtures at 62 .degree.C
journal, November 1995
- Gasteiger, Hubert A.; Markovic, Nenad M.; Ross, Philip N.
- The Journal of Physical Chemistry, Vol. 99, Issue 45
Advanced Electrodes for Solid Acid Fuel Cells by Platinum Deposition on CsH 2 PO 4
journal, April 2011
- Papandrew, Alexander B.; Chisholm, Calum R. I.; Elgammal, Ramez A.
- Chemistry of Materials, Vol. 23, Issue 7
Activity and Evolution of Vapor Deposited Pt-Pd Oxygen Reduction Catalysts for Solid Acid Fuel Cells
journal, December 2012
- Papandrew, Alexander B.; Chisholm, Calum R. I.; Zecevic, Strahinja K.
- Journal of The Electrochemical Society, Vol. 160, Issue 2
Electrochemical Hydrogen Separation via Solid Acid Membranes
journal, January 2014
- Papandrew, Alexander B.; Wilson, David L.; M. Cantillo, Nelly
- Journal of The Electrochemical Society, Vol. 161, Issue 5
Parameter-free calculations of X-ray spectra with FEFF9
journal, January 2010
- Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 21
Experimental Methods for Quantifying the Activity of Platinum Electrocatalysts for the Oxygen Reduction Reaction
journal, August 2010
- Garsany, Yannick; Baturina, Olga A.; Swider-Lyons, Karen E.
- Analytical Chemistry, Vol. 82, Issue 15
Electrochemical surface area measurements of platinum- and palladium-based nanoparticles
journal, June 2013
- Shao, Minhua; Odell, Jonathan H.; Choi, Sang-Il
- Electrochemistry Communications, Vol. 31
Structural dependence of oxygen reduction reaction on palladium nanocrystals
journal, January 2011
- Shao, Minhua; Yu, Taekyung; Odell, Jonathan H.
- Chemical Communications, Vol. 47, Issue 23
Effects of annealing treatment and pH on preparation of citrate-stabilized PtRu/C catalyst
journal, November 2006
- Xu, Yuqin; Xie, Xiaofeng; Guo, Jianwei
- Journal of Power Sources, Vol. 162, Issue 1
In situ analysis of optimum surface atom coordination for Pt nanoparticle oxygen reduction electrocatalysts
journal, December 2013
- St. John, Samuel; Angelopoulos, Anastasios P.
- Electrochimica Acta, Vol. 112
Synthesis and Characterization of Electrocatalytically Active Platinum Atom Clusters and Monodisperse Single Crystals
journal, July 2010
- St. John, Samuel; Dutta, Indrajit; P. Angelopoulos, Anastasios
- The Journal of Physical Chemistry C, Vol. 114, Issue 32
Ruthenium as a CO-tolerant hydrogen oxidation catalyst for solid acid fuel cells
journal, January 2015
- Papandrew, Alexander B.; Atkinson III, Robert W.; Unocic, Raymond R.
- Journal of Materials Chemistry A, Vol. 3, Issue 7
Interaction of a Nanosized Pd Catalyst with Active C from the Carbon Support: An Advanced in Situ XRD Study
journal, December 2010
- Vogel, Walter
- The Journal of Physical Chemistry C, Vol. 115, Issue 5
The irreversible formation of palladium carbide during hydrogenation of 1-pentyne over silica-supported palladium nanoparticles: in situ Pd K and L3 edge XAS
journal, January 2012
- Tew, Min Wei; Nachtegaal, Maarten; Janousch, Markus
- Physical Chemistry Chemical Physics, Vol. 14, Issue 16
Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes
journal, January 2010
- Sheng, Wenchao; Gasteiger, Hubert A.; Shao-Horn, Yang
- Journal of The Electrochemical Society, Vol. 157, Issue 11
Correlating the hydrogen evolution reaction activity in alkaline electrolytes with the hydrogen binding energy on monometallic surfaces
journal, January 2013
- Sheng, Wenchao; Myint, MyatNoeZin; Chen, Jingguang G.
- Energy & Environmental Science, Vol. 6, Issue 5
Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations
journal, October 2010
- Skúlason, Egill; Tripkovic, Vladimir; Björketun, Mårten E.
- The Journal of Physical Chemistry C, Vol. 114, Issue 42
The study of hydrogen sorption in palladium limited volume electrodes (Pd-LVE)
journal, October 2000
- Czerwiński, Andrzej; Kiersztyn, Iwona; Grdeń, Michał
- Journal of Electroanalytical Chemistry, Vol. 492, Issue 2
Hydrogen absorption in palladium electrodes in alkaline solutions
journal, September 1992
- Enyo, M.; Biswas, P. C.
- Journal of Electroanalytical Chemistry, Vol. 335, Issue 1-2
Studying the oxygen reduction and hydrogen oxidation reactions under realistic fuel cell conditions
journal, November 2008
- Kucernak, Anthony R.; Toyoda, Eishiro
- Electrochemistry Communications, Vol. 10, Issue 11
Electrocatalysis under Conditions of High Mass Transport: Investigation of Hydrogen Oxidation on Single Submicron Pt Particles Supported on Carbon
journal, September 2004
- Chen, Shengli; Kucernak, Anthony
- The Journal of Physical Chemistry B, Vol. 108, Issue 37
Works referencing / citing this record:
High-Performance Hydroxide Exchange Membrane Fuel Cells through Optimization of Relative Humidity, Backpressure and Catalyst Selection
journal, January 2019
- Wang, Teng; Shi, Lin; Wang, Junhua
- Journal of The Electrochemical Society, Vol. 166, Issue 7
Engineering heterometallic bonding in bimetallic electrocatalysts: towards optimized hydrogen oxidation and evolution reactions
journal, January 2020
- Huang, Chiu-Ping; Tsai, Meng-Che; Wang, Xiao-Ming
- Catalysis Science & Technology, Vol. 10, Issue 3
Origin of Superior HOR/HER Activity of Bimetallic Pt-Ru Catalysts in Alkaline Media Identified via Ru@Pt Core-Shell Nanoparticles
journal, January 2018
- Schwämmlein, Jan N.; Stühmeier, Björn M.; Wagenbauer, Klaus
- Journal of The Electrochemical Society, Vol. 165, Issue 5
A Pd/C-CeO 2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells
journal, April 2016
- Miller, Hamish A.; Lavacchi, Alessandro; Vizza, Francesco
- Angewandte Chemie International Edition, Vol. 55, Issue 20
Recent progress in the structure control of Pd–Ru bimetallic nanomaterials
journal, July 2016
- Wu, Dongshuang; Kusada, Kohei; Kitagawa, Hiroshi
- Science and Technology of Advanced Materials, Vol. 17, Issue 1
The Comparability of Pt to Pt-Ru in Catalyzing the Hydrogen Oxidation Reaction for Alkaline Polymer Electrolyte Fuel Cells Operated at 80 °C
journal, January 2019
- Li, Qihao; Peng, Hanqing; Wang, Yingming
- Angewandte Chemie International Edition, Vol. 58, Issue 5
Impact of the Anode Catalyst Layer Design on the Performance of H 2 O 2 -Direct Borohydride Fuel Cells
journal, January 2019
- Hjelm, Rachel M. E.; Lafforgue, Clémence; Atkinson, Robert W.
- Journal of The Electrochemical Society, Vol. 166, Issue 15
The Hydrogen Oxidation Reaction in Alkaline Medium: An Overview
journal, March 2019
- Campos-Roldán, Carlos Augusto; Alonso-Vante, Nicolas
- Electrochemical Energy Reviews, Vol. 2, Issue 2
Uniform Pd 0.33 Ir 0.67 nanoparticles supported on nitrogen-doped carbon with remarkable activity toward the alkaline hydrogen oxidation reaction
journal, January 2019
- Cong, Yuanyuan; McCrum, Ian T.; Gao, Xueqiang
- Journal of Materials Chemistry A, Vol. 7, Issue 7
Evaluating Hydrogen Evolution and Oxidation in Alkaline Media to Establish Baselines
journal, January 2018
- Alia, Shaun M.; Pivovar, Bryan S.
- Journal of The Electrochemical Society, Vol. 165, Issue 7
A Pd/C-CeO 2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells
journal, April 2016
- Miller, Hamish A.; Lavacchi, Alessandro; Vizza, Francesco
- Angewandte Chemie, Vol. 128, Issue 20
Recent progress in the structure control of Pd–Ru bimetallic nanomaterials
journal, July 2016
- Wu, Dongshuang; Kusada, Kohei; Kitagawa, Hiroshi
- Science and Technology of Advanced Materials, Vol. 17, Issue 1